KR20220030273A - Process for preparing multifunctional catalyst from heteropolyacid on zeolite for upgrading pyrolysis oil, said catalyst and process for upgrading - Google Patents

Abstract

A method of preparing a multifunctional catalyst for upgrading a pyrolysis oil comprises contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, the first metal catalyst precursor, a second The metal catalyst precursor or both comprise a heteropolyacid. The step of contacting the zeolite support with the solution deposits or adsorbs the first metal catalyst precursor and the second catalyst precursor on the outer surface and the pore surface of the zeolite support to prepare a multifunctional catalyst precursor. The method comprises the steps of removing excess solution from the multifunctional catalyst precursor and calcining the multifunctional catalyst precursor to include at least a first metal catalyst and a second metal catalyst deposited on the outer and pore surfaces of a zeolite support. It further comprises the step of preparing the catalyst.

Description

Process for preparing multifunctional catalyst from heteropolyacid on zeolite for upgrading pyrolysis oil, said catalyst and process for upgrading

Cross-referencing of related applications

This application claims priority to U.S. Patent No. 16/502,633, filed July 3, 2019, the entire contents of which are incorporated herein by reference.

technical field

The present specification relates generally to a multi-functional catalyst for upgrading pyrolysis oil and a method for preparing the multi-functional catalyst.

Crude oil can be converted into useful chemical intermediates and products through one or more hydrotreating processes. The hydrotreating process may include steam cracking, wherein the larger hydrocarbons in the crude oil are cracked to form smaller hydrocarbons. The steam cracking unit produces a bottoms stream, which is referred to as pyrolysis oil. The pyrolysis oil may include an increased concentration of aromatics compared to the crude oil feedstock. In many crude oil processing plants, this pyrolysis oil is burned as a fuel. However, aromatic compounds in pyrolysis oils can be converted into useful chemical intermediates and building blocks. For example, aromatics from pyrolysis oil can be converted to xylene, which can be a starting material for making terephthalic acid, which can then be used to make polyester. The aromatic compounds in the pyrolysis oil can be used to prepare many other useful aromatic intermediates. The market demand for these useful aromatic intermediates continues to grow.

summary

Accordingly, there is a continuing need for improved multifunctional catalysts for upgrading pyrolysis oils. The pyrolysis oil from the steam cracking process can be upgraded by contacting the pyrolysis oil with a catalyst that can be used to convert the multi-ring aromatics in the pyrolysis oil to one or more C6 to C8 aromatics to prepare useful aromatic intermediates and , the aromatic compound may include benzene, toluene, ethylbenzene, xylene, other aromatic compounds, or a combination thereof. Existing catalysts that may be used to upgrade pyrolysis oils may include multi-metal hydrocracking catalysts having two or more metals supported on a catalyst support. Such multi-metal hydrocracking catalysts are typically prepared from conventional metal precursors such as metalate hydrates, metal nitrates and other conventional metal precursors.

With these multi-metal hydrogencracking catalysts prepared from conventional metal precursors, macroaromatic compounds (greater than 8 carbon atoms) can be produced at reaction temperatures ranging from 380 degrees Celsius (°C) to 400°C and from 6 megapascals (MPa) to It can be converted into C6 to C8 aromatic compounds at a pressure of 8 MPa. Maintaining the pressure in the range of 6 MPa to 8 MPa may require higher pressure resistance of the facility and may consume a greater amount of energy compared to lower pressure systems. In other words, the use of conventional multi-metal hydrocracking catalysts to upgrade pyrolysis oils requires expensive equipment believed to be for higher operating pressures, and requires higher amounts of energy to maintain pressures above 6 MPa. can be consumed Lowering the pressure below 6 MPa can substantially reduce the yield of C6 to C8 aromatics when upgrading using these existing multi-metal hydrocracking catalysts prepared from conventional metal catalyst precursors.

The present disclosure provides a multifunctional catalyst for upgrading a pyrolysis oil prepared using a heteropolyacid for at least one metal precursor, a method for preparing the multifunctional catalyst and upgrading a pyrolysis oil using the multifunctional catalyst. it's about how The multifunctional catalyst of the present disclosure produces higher yields of C6 to C8 aromatics from upgrading the pyrolysis oil at reduced reaction pressure compared to upgrading the pyrolysis oil using a conventional multi-metal hydrocracking catalyst can do. The multifunctional catalyst of the present disclosure may be prepared by contacting a zeolite support with a first metal catalyst precursor and a second metal catalyst precursor, wherein at least one of the first or second metal catalyst precursor is a heteropolyacid. Heteropolyacids are compounds comprising at least acid hydrogen, a transition metal, at least one heteroatom and oxygen. The preparation of multifunctional catalysts using heteropolyacids for at least one metal precursor instead of conventional metal precursors results in higher yields at reduced reaction pressure compared to multi-metal hydrocracking catalysts currently used to upgrade pyrolysis oils. It has been found to prepare multifunctional catalysts that yield C6 to C8 aromatics. Improved yield and reduced operating pressure can increase efficiency and reduce capital and operating costs of the process for upgrading the pyrolysis oil.

According to one or more aspects of the present disclosure, a method of preparing a multifunctional catalyst for upgrading a pyrolysis oil comprises contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor. . The first metal catalyst precursor, the second metal catalyst precursor, or both may comprise a heteropoly acid, wherein the contacting is accomplished by depositing the first metal catalyst precursor and the second catalyst precursor on the outer surface and the pore surface of the zeolite support. Functional catalyst precursors can be prepared. The method comprises the steps of removing excess solution from the multifunctional catalyst precursor and calcining the multifunctional catalyst precursor to include at least a first metal catalyst and a second metal catalyst deposited on the outer and pore surfaces of a zeolite support. It may further comprise the step of preparing a catalyst. In an aspect of the present disclosure, the multifunctional catalyst for upgrading pyrolysis oil may be a multifunctional catalyst prepared by the method of the present disclosure.

According to one or more other aspects of the present disclosure, a method for upgrading a pyrolysis oil comprises subjecting the pyrolysis oil to a mild reaction condition comprising a reaction temperature of less than 500 degrees Celsius (° C.) and a pressure of less than 6 megapascals (MPa). contacting with a functional catalyst. The pyrolysis oil may include multi-ring aromatics. The multifunctional catalyst can be prepared by contacting a zeolite with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, wherein the first metal catalyst precursor, the second metal catalyst precursor, or both form a heteropolyacid wherein the contacting step causes the first metal catalyst precursor and the second catalyst precursor to be deposited on the outer surface and the pore surface of the zeolite support to prepare a multifunctional catalyst precursor. The process for preparing the multi-functional catalyst may further comprise removing the excess solution from the multi-functional catalyst precursor and calcining the multi-functional catalyst precursor to prepare the multi-functional catalyst. The multifunctional catalyst may comprise at least a first metal catalyst and a second metal catalyst supported on a zeolite support. Contacting the pyrolysis oil with the multifunctional catalyst at the above reaction conditions may convert at least some of the multi-ring aromatic compounds in the pyrolysis oil to one or more C6 to C8 aromatic compounds.

Additional features and advantages of the above-described embodiments will be set forth in the Detailed Description of the Invention which follows, some of which will be readily apparent to those skilled in the art from this Description, or those described above, including the following Detailed Description, the claims and the appended drawings. It will be appreciated by practicing the embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS The following detailed description of certain embodiments of the present disclosure is best understood when read in conjunction with the following drawings, in which like structures are denoted by like reference numerals;
1 schematically illustrates a reactor system for upgrading pyrolysis oil in accordance with one or more embodiments described in the present disclosure;
2 schematically depicts an exemplary composition of a pyrolysis oil obtained from a steam cracking process for steam cracking crude oil in accordance with one or more embodiments described in the present disclosure;
3 schematically depicts a reactor system for upgrading a model pyrolysis oil in an example in accordance with one or more embodiments described in the present disclosure.
For purposes of describing the simplified schematics and descriptions of Figures 1 and 3, there are a number of valves, temperature sensors, flow meters, pressure regulators, electronic controllers, pumps, etc. not included. Additionally, accessory components normally involved in typical chemical processing operations, such as valves, pipes, pumps, agitators, heat exchangers, meters, internal vessel structures, or other subsystems, may not be shown. Although not shown, these components are to be understood as being within the spirit and scope of the disclosed embodiments. However, operational components such as those described in this disclosure may be added to the embodiments described in this disclosure.
Arrows in the figure refer to process streams. However, arrows may equally refer to transfer lines that may serve to transfer process streams between two or more system components. Additionally, arrows connected to system components may define inlets or outlets in each particular system component. The direction of the arrow generally corresponds to the main direction of movement of the stream material retained within the physical transfer line indicated by the arrow. Additionally, arrows that do not connect two or more system components may represent a product stream exiting the depicted system or a system inlet stream entering the depicted system. The product stream may be further processed in a companion chemical treatment system or may be commercialized as an end product.
In addition, arrows in the figures may schematically depict process steps for moving a stream from one system component to another. For example, an arrow pointing from one system component to another system component may represent "passing" the effluent of a system component to another system component, and may be "exhausted" or removed from one system component. "introducing" the contents of the process stream being processed and the contents of that product stream into other system components.
When two or more lines intersect in the schematic flow diagrams of FIGS. 1 and 3 , it is to be understood that two or more process streams are “mixed” or “combined”. Mixing or combining may also include mixing by introducing both streams directly into the same system component, such as a separation device, reactor or other system component. For example, where two streams are shown to be combined just prior to entering the system component, it is to be understood that the streams may be equally introduced into the system component separately and mixed within the system component.
Reference will now be made in more detail to various embodiments, some of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

Embodiments of the present disclosure relate to multifunctional catalysts for upgrading pyrolysis oils. The multifunctional catalyst comprises a plurality of metal catalysts supported on a zeolite support. The multifunctional catalyst of the present disclosure can be prepared using a heteropolyacid for at least one metal catalyst precursor. The multifunctional catalyst for upgrading the pyrolysis oil of the present disclosure prepared using a heteropolyacid for the metal catalyst precursor provides a higher yield of useful aromatic compounds such as benzene, toluene, ethylbenzene and Xylene may be provided. In addition, the multifunctional catalyst for upgrading the pyrolysis oil can allow the upgrading of the pyrolysis oil to be performed at a lower reaction pressure compared to existing commercially available catalysts for upgrading the pyrolysis oil.

As used herein, the term “C6 to C8 aromatic compound” may refer to one or more compounds having a substituted or unsubstituted aromatic ring and having 6 to 8 carbon atoms. The term “BTEX” may refer to any combination of benzene, toluene, ethylbenzene, para -xylene, meta -xylene and ortho -xylene.

As used herein, the term "xylene", when used without indication of isomers such as the prefix para , meta or ortho , is meta -xylene, ortho -xylene, para -xylene and these xylenes. may refer to one or more of a mixture of isomers.

As used in this disclosure, the terms “upstream” and “downstream” refer to the relative position of device operation to the direction of process stream flow. A first unit operation of the system is considered "upstream" of a second unit operation if the process stream flowing through the system encounters a first unit operation before it encounters a second unit operation. Likewise, a second unit operation is considered “downstream” of the first unit operation if the process stream flowing through the system encounters a first unit operation before it encounters a second unit operation.

Referring now to FIG. 1 , there is schematically shown a system 10 for upgrading pyrolysis oil 12 . The system 10 for upgrading the pyrolysis oil 12 may include a reactor apparatus 20 and a separation apparatus 30 downstream of the reactor apparatus 20 . Reactor apparatus 20 may include one or more reactors and may be operated such that pyrolysis oil 12 is contacted with catalyst in reaction zone 14 to produce upgraded effluent 22 . The catalyst may be a multifunctional catalyst of the present disclosure. The upgraded effluent 22 may be passed to a separation device 30 , which may include one or more separation processes or device operations. Separation apparatus 30 may be operable to separate upgraded effluent 22 into one or a plurality of product streams, eg, a BTEX-containing stream and a higher boiling point fraction 34 . Separation device 30 is shown in FIG. 1 as separating upgraded effluent 22 into a C6 to C8 aromatics stream 32 and a higher boiling fraction 34, while separation device 30 separates upgraded effluent 22 ) into a plurality of product streams, one of which may comprise a C6 to C8 aromatic stream (32).

The pyrolysis oil 12 may be a stream from a hydrocarbon processing plant rich in aromatics, such as multi-ring aromatics. In some embodiments, the pyrolysis oil may be a bottoms stream from a steam cracking process. The pyrolysis oil 12 may include mono-aromatic compounds and multi-aromatic compounds. Multi-aromatic compounds may include aromatic compounds comprising 2, 3, 4, 5, 6, 7, 8 or more than 8 aromatic ring structures. The pyrolysis oil 12 may also include other components such as, but not limited to, saturated hydrocarbons. Referring to FIG. 2 , the composition of a typical pyrolysis oil prepared by steam cracking crude oil from Saudi Arabia is shown. As shown in Figure 2, pyrolysis oils include mono-aromatic, di-aromatic, tri-aromatic, tetra-aromatic, penta-aromatic, hexa-aromatic and aromatic compounds having at least 7 aromatic rings (hepta and superaromatic). can do. The pyrolysis oil may contain high concentrations of di-aromatics and aromatics having more than 7 aromatic rings as indicated in FIG. 2 . In some embodiments, the pyrolysis oil rich in multi-aromatic compounds is at least 50 weight percent (wt. %) multi-aromatic compounds, e.g., at least 60 weight percent, at least 65 weight percent, 70 weight percent, based on the unit weight of the pyrolysis oil. at least 75% by weight or even at least 80% by weight of the multi-aromatic compound. The pyrolysis oil may also have low concentrations of sulfur and sulfur compounds. The pyrolysis oil may have a concentration of sulfur and sulfur-containing compounds of up to 500 parts per million (ppmw) by weight, for example up to 400 ppmw or even up to 300 ppmw.

The multi-aromatics in the pyrolysis oil can be upgraded to C6 to C8 aromatics through contact with a catalyst at the reaction temperature and pressure. The conversion of di-aromatics and multi-aromatics to C6 to C8 aromatics, such as benzene, toluene, ethylbenzene and xylene, is a complex reaction that can involve multiple simultaneous and selective reactions, the total being selective hydrogenation of one aromatic ring of one of the other compounds, subsequent ring opening of a saturated naphthalene-based ring, hydrogen-dealkylation and transalkylation.

This complex, co-occurring continuous reaction to upgrade pyrolysis oil can be promoted using a multi-metal catalyst with at least a catalytic transition metal. In a typical upgrade process, the catalyst used to upgrade the pyrolysis oil may be a multi-metal hydrocracking catalyst. Such multi-metal hydrocracking catalysts are usually synthesized using conventional metal precursors, for example metallate hydrates, metal nitrates, metal carbonates, metal hydroxides, other conventional metal precursors or combinations of these conventional metal precursors.

With these multi-metal hydrogencracking catalysts prepared from conventional metal precursors, macroaromatics (greater than 8 carbon atoms) are reacted at a reaction temperature ranging from 380°C to 400°C and pressures from 6 megapascals (MPa) to 8 MPa. to C6 to C8 aromatic compounds such as, but not limited to, benzene, toluene, ethylbenzene or xylene (BTEX). Maintaining the pressure in the range of 6 MPa to 8 MPa may require higher pressure tolerance of the plant and may consume a greater amount of energy compared to reactions conducted at lower reaction pressures. In other words, the use of existing multi-metal hydrocracking catalysts to upgrade pyrolysis oils may require expensive equipment believed to be for higher operating pressures, and require larger amounts of equipment to maintain pressures above 6 MPa. energy can be consumed. In addition, the yield of C6 to C8 aromatic compounds using this conventional multi-metal hydrogen cracking catalyst is low. Lowering the pressure below 6 MPa can further reduce the yield of C6 to C8 aromatics when upgrading using existing multi-metal hydrocracking catalysts.

As previously discussed, the present disclosure relates to a multifunctional catalyst for upgrading pyrolysis oil, wherein the multifunctional catalyst is prepared by using one or more heteropolyacids as a metal precursor for one or more metal catalysts of the multifunctional catalyst. . A method of preparing a multifunctional catalyst for upgrading a pyrolysis oil may comprise contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, the first metal catalyst precursor, the second The two metal catalyst precursor or both comprise a heteropolyacid. The step of contacting the zeolite support with the solution allows the first metal catalyst precursor and the second catalyst precursor to be deposited or adsorbed on the outer surface and the pore surface of the zeolite support to prepare a multifunctional catalyst precursor. The method comprises the steps of removing excess solution and solvent from the multifunctional catalyst precursor, and calcining the multifunctional catalyst precursor to deposit at least a first metal catalyst and a second metal catalyst on the outer and pore surfaces of the zeolite support. It may further comprise the step of preparing a multifunctional catalyst.

The multifunctional catalyst prepared by the method of the present disclosure can increase the yield of BTEX from upgrading the pyrolysis oil compared to the existing multi-metal hydrocracking catalyst. In addition, as compared with the existing multi-metal hydrocracking catalyst, the multi-vapor catalyst prepared by the method of the present disclosure also has the same reaction temperature and reduced reaction pressure, for example, 5 Mpa or less, with the upgrade of the pyrolysis oil. to be carried out at a reaction pressure of The reduced reaction pressure possible due to the multifunctional catalyst of the present disclosure can reduce the operating cost and capital of a system for upgrading the pyrolysis oil.

A method of preparing the multifunctional catalyst may include providing a zeolite support. The zeolite support may be a nano-zeolite having an average pore size of 2 micrometers (μm) or even 1 μm or less. The zeolite support may have a molar ratio of silica (SiO ₂ ) to alumina (Al ₂ O ₃ ) of 10 or more, for example, 20 or more, 30 or more, 40 or more, 50 or more, or 60 or more. The zeolite support may have a molar ratio of SiO ₂ to Al ₂ O ₃ of 70 or less, for example 60 or less, 50 or less, 40 or less, 30 or less or even 20 or less. The zeolite support may have a molar ratio of SiO ₂ to Al ₂ O ₃ of from 10 to 70. In some embodiments, the zeolite support is 10 to 60, 10 to 50, 10 to 40, 20 to 70, 20 to 60, 20 to 50, 20 to 40, 30 to 70, 30 to 60, 30 to 50, 40 to It may have a molar ratio of SiO ₂ to Al ₂ O ₃ of 70, 40 to 60, 50 to 70, or 10 to 30. In some embodiments, the zeolite support may be a beta zeolite support. In some embodiments, the zeolite support may be a nano-beta zeolite support having an average pore size of 2 μm or less.

The method for preparing the multifunctional catalyst for upgrading the pyrolysis oil may be a wet impregnation method wherein the at least one metal catalyst precursor is a heteropolyacid. The method may include contacting the zeolite support with a solution comprising at least a first metal catalyst precursor, a second metal catalyst precursor and a solvent. The solution may also include a phosphorus-containing compound. The first metal catalyst precursor may include a first metal, and the second metal catalyst precursor may include a second metal different from the first metal. The first and second metals may be transition metals, such as, but not limited to, transition metals of groups 5, 6, 7, 8, 9 and 10 of the International Union of Pure and Applied Chemistry (IUPAC) Periodic Table of Elements. In some embodiments, the first metal of the first metal catalyst precursor may be a metal selected from cobalt, molybdenum, vanadium, or combinations thereof. In some embodiments, the second metal of the second metal catalyst precursor may be a metal selected from cobalt, molybdenum, vanadium, or combinations thereof, and may be different from the first metal.

The first metal catalyst precursor, the second metal catalyst precursor, or both may be a heteropolyacid. Heteropolyacids include cobalt, molybdenum or a combination of cobalt and molybdenum; at least one heteroatom selected from phosphorus (P), silicon (Si), arsenic (As), germanium (Ge), or a combination thereof; and one or more than one acidic hydrogen. As used herein, the term “acidic hydrogen” may refer to a hydrogen atom of a heteropolyacid that may have a tendency to dissociate from the heteropolyacid in solution to form zwitterions. The heteropolyacid may also include oxygen. Heteropolyacids suitable for the first metal catalyst precursor, the second metal catalyst precursor or both have a keggin structure having the general formula XM ₁₂ O ₄₀ ^n- or a Dawson structure having the general formula XM ₁₈ O ₈₂ ^n- structure), wherein X is a heteroatom selected from phosphorus, silicon, arsenic, germanium, or a combination thereof; M is molybdenum and optionally one or more of cobalt, vanadium, or combinations thereof; n- is an integer representation of the charge of the heteropolyacid anion. Examples of heteropolyacids include phosphormolybdic heteropolyacid (H ₃ PMo ₁₂ O ₄₀ ), silicomolybdic heteropolyacid (H ₄ SiMo ₁₂ O ₄₀ ), decamolybdiccobaltate heteropolyacid )(H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ]), H ₄ [PCoMo ₁₁ O ₄₀ ], H ₄ [PVMo ₁₁ O ₄₀ ], H ₅ [PV ₂ Mo ₁₀ O ₄₀ ], H ₇ [PV ₄ Mo ₈ O ₄₀ ], H ₉ [PV ₆ Mo ₆ O ₄₀ ], H ₃ [AsMo ₁₂ O ₄₀ ], H ₄ [AsCoMo ₁₁ O ₄₀ ], H ₅ [AsCo ₂ Mo ₁₀ O ₄₀ ], H ₄ [AsVMo ₁₁ O ₄₀ ], H ₅ [AsV ₂ Mo ₁₀ O ₄₀ ], H ₇ [AsV ₄ Mo ₈ O ₄₀ ], H ₉ [AsV ₆ Mo ₆ O ₄₀ ], H ₅ [SiCoMo ₁₁ O ₄₀ ], H ₆ [ SiCo ₂ Mo ₁₀ O ₄₀ ], H ₅ [SiVMo ₁₁ O ₄₀ ], H ₆ [SiV ₂ Mo ₁₀ O ₄₀ ], H ₁₀ [SiV ₆ Mo ₆ O ₄₀ ], H ₆ [P ₂ Mo ₁₈ O ₈₂ ], other heteropolyacids, salts of these heteropolyacids, or combinations of heteropolyacids. Salts of these heteropolyacids may include alkali metal salts, alkaline earth metal salts, nitrates, sulfates or other salts of heteropolyacids. The alkali metal may include sodium, potassium, rubidium, cesium, or combinations thereof. Alkaline earth metals may include, but are not limited to, magnesium, calcium, or combinations thereof. In some embodiments, the heteropolyacid can include a phosphomolybdic heteropolyacid having the formula H ₃ [PMo ₁₂ O ₄₀ ]. In some embodiments, the heteropolyacid can include a decamolybdodicobaltate heteropolyacid having the formula H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ]. In some embodiments, the heteropolyacid can be a silicomolybdic heteropolyacid having the formula H ₄ [SiMo ₁₂ O ₄₀ ]. In some embodiments, the first metal catalyst precursor, the second catalyst precursor, or both can be a metal salt of a heteropoly acid, for example an alkali metal salt or an alkaline metal salt of a heteropoly acid.

As previously described, the first metal catalyst precursor, the second metal catalyst precursor, or both may be a heteropolyacid. In some embodiments, the first metal catalyst precursor may comprise a heteropolyacid and the second metal catalyst precursor may comprise a non-heteropolyacid precursor. In some embodiments, both the first metal catalyst precursor and the second metal catalyst precursor may include a heteropolyacid. In some embodiments, the first metal catalyst precursor may comprise a first heteropolyacid and the second metal catalyst precursor may comprise a second heteropolyacid different from the first heteropolyacid. For example, in some embodiments, the first metal catalyst precursor may comprise a first heteropolyacid comprising molybdenum as a metal, and the second metal catalyst precursor may comprise a second heteropolyacid comprising cobalt as a metal. . In some embodiments, the first metal catalyst precursor and the second metal catalyst precursor may comprise the same heteropolyacid, wherein the heteropolyacid comprises a first metal, a second metal different from the first metal, and at least one heteroatom there is. For example, in some embodiments, the solution may include a decamolybdiccobaltate heteropolyacid having the formula H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ], comprising both cobalt and molybdenum, wherein the first It can serve as both a metal catalyst precursor and a second metal catalyst precursor.

In some embodiments, either the first metal catalyst precursor or the second metal precursor may include a non-heteropoly acid metal catalyst precursor, such as metalate hydrate, metal nitrate and other non-heteropoly acid precursors. The solution may also include a phosphorus-containing compound, such as but not limited to phosphoric acid, phosphorous acid or other phosphorus-containing compound.

The first metal catalyst precursor and the second metal catalyst precursor may be dispersed or dissolved in a solvent to form a solution. The solvent may be water. The solvent may also include one or more organic solvents such as, but not limited to, organic alcohols or other organic solvents. One or more than one heteropolyacid may be dehydrated prior to combining the heteropolyacid with a solvent to form a solution. The solution may have a concentration of the first metal catalyst precursor sufficient to cause the first metal catalyst precursor to be deposited or adsorbed onto the outer surface and the pore surface of the zeolite support. The solution may have at least 1 wt%, at least 2 wt%, at least 5 wt%, or even at least 10 wt% of the first metal catalyst precursor prior to being contacted with the zeolite support, based on the total weight of the solution. The solution may have up to 20 wt%, up to 15 wt%, or even up to 12 wt% of the first metal catalyst precursor, based on the total weight of the solution prior to being contacted with the zeolite support. In some embodiments, the solution comprises 1% to 20% by weight of the first metal catalyst precursor, such as 1% to 15%, 1% to 10% by weight, based on the total weight of the solution prior to being contacted with the zeolite support. wt%, 1 wt% to 5 wt%, 2 wt% to 20 wt%, 2 wt% to 15 wt%, 2 wt% to 10 wt% or 2 wt% to 5 wt% of the first metal catalyst precursor can do.

The solution may have a concentration of the second metal catalyst precursor sufficient to cause the second metal catalyst precursor to be deposited or adsorbed on the outer surface and the pore surface of the zeolite support. The solution may have at least 1 wt%, at least 2 wt%, at least 5 wt% or even at least 10 wt% of the second metal catalyst precursor, based on the total weight of the solution prior to being contacted with the zeolite support. The solution may have up to 20 wt %, up to 15 wt % or even up to 12 wt % of the second metal catalyst precursor, based on the total weight of the solution prior to being contacted with the zeolite support. In some embodiments, the solution comprises 1% to 20% by weight of the second metal catalyst precursor, such as 1% to 15%, 1% to 10% by weight, based on the total weight of the solution prior to being contacted with the zeolite support. wt%, 1 wt% to 5 wt%, 2 wt% to 20 wt%, 2 wt% to 15 wt%, 2 wt% to 10 wt% or 2 wt% to 5 wt% of the second metal catalyst precursor can do.

A solution can be prepared and the zeolite support can be contacted with the solution at ambient conditions. The solution may be mixed for a period of time before the zeolite support is contacted with the solution. The mixture comprising the zeolite support dispersed in solution may be mixed for a period of time long enough to provide sufficient adsorption or deposition of the first metal catalyst precursor and the second metal catalyst precursor on the outer and pore surfaces of the zeolite support. . Contacting the zeolite support with a solution containing the first metal catalyst precursor and the second metal catalyst precursor may result in obtaining a mixture of the multifunctional catalyst precursor dispersed in the solution. The mixture may also include residual first metal catalyst precursor, second metal catalyst precursor and any other constituents that are not adsorbed on the outer surface and pore surface of the zeolite support. The multifunctional catalyst precursor may comprise at least a first metal catalyst precursor and a second metal catalyst precursor deposited or adsorbed on the outer surface or pore surface of the zeolite support.

As previously discussed, after contacting the zeolite support with a solution comprising a first metal catalyst precursor and a second metal catalyst precursor, excess liquid, e.g., solution or solvent, is removed from the mixture to prepare the multifunctional catalyst precursor. can Removing the liquid component may include removing excess liquid from the multi-functional catalyst precursor and drying the multi-functional catalyst precursor. The step of removing excess liquid from the multifunctional catalyst precursor may include subjecting the mixture to decantation, filtration, vacuum filtration, or a combination thereof. In some embodiments, removing liquid from the mixture may comprise vacuum filtration of the mixture at a temperature between 25°C and 90°C. Drying the multifunctional catalyst precursor may include maintaining the multifunctional catalyst precursor at a temperature above the boiling point temperature of the solvent, for example, at a temperature of 90°C to 200°C. The drying step may be conducted for a drying period sufficient to remove the solvent to a level of less than 1% by weight of the total weight of the multifunctional catalyst precursor. The drying period may be from 1 hour to 24 hours, for example from 2 hours to 12 hours. The drying step may remove additional solvent from the multifunctional catalyst through evaporation of the solvent. In some embodiments, the solvent may be water and the drying step may include maintaining the multifunctional catalyst precursor at a temperature of 100° C. or higher for a drying period of at least 1 hour.

As previously discussed, the method may further comprise calcining the multifunctional catalyst precursor to prepare the multifunctional catalyst of the present disclosure. The step of calcining the multifunctional catalyst precursor may be performed after removal of excess solution and solvent from the multifunctional catalyst precursor. The multifunctional catalyst precursor may be calcined at a temperature of 500° C. to 600° C. for a calcination period of 4 to 6 hours to prepare the multifunctional catalyst.

The method described in the present disclosure is based on wet impregnation of first and second catalyst precursors on the outer surface and pore surface of a zeolite support. It is understood that other methods of preparing multifunctional catalysts using heteropolyacids for one or more than one metal catalyst precursor may also be used. Such methods of making multifunctional catalysts for upgrading pyrolysis oils may include, but are not limited to, for example, co-precipitation methods.

The multifunctional catalyst for upgrading the pyrolysis oil produced by the method described in the present disclosure may comprise at least a first metal catalyst and a second metal catalyst supported on the outer surface and the pore surface of the zeolite support. The first metal catalyst and the second metal catalyst may include any metal previously described in this disclosure for the first metal catalyst and the second metal catalyst, respectively. The multifunctional catalyst may also comprise a heteroatom from a heteropolyacid supported on the outer surface or pore surface of the zeolite support - such as but not limited to phosphorus, silicon, arsenic, or combinations thereof. In some embodiments, the first metal catalyst can be molybdenum, the second metal catalyst can be cobalt or vanadium, and at least the molybdenum is provided as a heteropolyacid. In some embodiments, cobalt may also be provided as a heteropolyacid that is the same or different from the heteropolyacid providing molybdenum. In some embodiments, the multifunctional catalyst may comprise molybdenum, cobalt and phosphorus supported on the outer surface and the pore surface of the nano beta zeolite support, wherein at least the molybdenum and phosphorus are provided as a heteropolyacid. In some embodiments, the multifunctional catalyst may comprise molybdenum, cobalt and silicon supported on the outer surface and pore surface of the nano beta zeolite support.

The use of a heteropolyacid for the at least one metal catalyst precursor can reduce the acidity and surface area of the multifunctional catalyst compared to commercially available catalysts for upgrading pyrolysis oils prepared using conventional metal catalyst precursors. The multifunctional catalyst for upgrading the pyrolysis oil of the present disclosure prepared using one or more than one heteropolyacid has the same metal catalyst species but lower than the acidity of existing commercially available catalysts prepared with conventional metal catalyst precursors. It may have acidity. The multifunctional catalyst is less than 10,000 micromolar ammonia/gram (μmol(NH ₃ )/g), less than 7,000 μmol(NH ₃ )/g, less than 5,000 μmol(NH ₃ )/g or even 4,000 μmol(NH ₃ )/g It may have the following acidity. In some embodiments, the multifunctional catalyst can have an acidity of from 1,000 μmol (NH ₃ )/g to 5,000 μmol (NH ₃ )/g.

Multifunctional catalyst for upgrading pyrolysis oil made with one or more than one heteropolyacid for at least one metal catalyst precursor compared to existing commercially available catalyst for upgrading pyrolysis oil made with conventional metal catalyst precursor Thus, the BET surface area can be reduced. As used herein, “BET surface area” refers to the average surface area of metal oxide particles as measured by the Brunauer Emmett Teller (BET) nitrogen absorption method according to ASTM D-6556. The multifunctional catalyst may have a BET surface area that is less than the BET surface area of the zeolite support prior to preparing the multifunctional catalyst. The multifunctional catalyst may have a BET surface area of 400 square meters/gram (m ² /g) or less, 375 m ² /g or less, 350 m ² /g or less, or even 325 m ² /g or less. In some embodiments, the multifunctional catalyst is 200 m ² /g to 400 m ² /g, for example 200 m ² /g to 375 m ² /g, 200 m ² /g to 350 m ² /g or 200 m It may have a BET surface area of ² /g to 325 m ² /g.

In some embodiments, the multifunctional catalyst for upgrading a pyrolysis oil is a multifunctional catalyst prepared by a process that can include contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor. It may be a catalyst. The first metal catalyst precursor, the second metal catalyst precursor, or both may comprise a heteropolyacid. Contacting the zeolite support with the solution allows the first metal catalyst precursor and the second catalyst precursor to be deposited on the outer and pore surfaces of the zeolite to prepare a multifunctional catalyst precursor. The zeolite support may include any zeolite support and may have any of the characteristics of the zeolite support previously described in this disclosure. The solution, the first metal catalyst precursor, the second metal catalyst precursor, and the one or more heteropolyacids may have any of the compositions, properties, or characteristics previously described for them in this disclosure. The method may further comprise removing the excess solution from the multi-functional catalyst precursor and calcining the multi-functional catalyst precursor to prepare the multi-functional catalyst. The contacting step, the removing the excess solution step and the calcining step may each be performed under any of the process conditions previously described in this disclosure for their respective process steps. The multifunctional catalyst prepared by the present method may comprise at least a first metal catalyst and a second metal catalyst deposited on the outer surface and the pore surface of the zeolite support. The multifunctional catalyst may have any composition or property previously described in this disclosure for the multifunctional catalyst.

The multifunctional catalyst prepared by the process described herein can be used to upgrade pyrolysis oils to one or more useful aromatic intermediates, such as, but not limited to, benzene, toluene, ethylbenzene, xylene, other aromatic compounds or their Combinations can be prepared. In some embodiments, a method for upgrading a pyrolysis oil can include contacting the pyrolysis oil with a multifunctional catalyst at mild reaction conditions comprising a reaction temperature of less than 500° C. and a pressure of less than 6 MPa. The pyrolysis oil may have any of the compositions or characteristics previously described in this disclosure for the pyrolysis oil. In some embodiments, the pyrolysis oil may include a multi-ring aromatic compound. The multi-functional catalyst may be prepared by a method or process for making the multi-functional catalyst described in this disclosure, and may have any of the properties, compositions, or attributes described in this disclosure for the multi-functional catalyst. In some embodiments, the multifunctional catalyst may be prepared by a process comprising contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, wherein the first metal catalyst precursor, the second The two metal catalyst precursor or both comprise a heteropolyacid. The contacting step allows the first metal catalyst precursor and the second catalyst precursor to be deposited or adsorbed on the outer surface and the pore surface of the zeolite to prepare a multifunctional catalyst precursor. The process for preparing the multi-functional catalyst may include removing excess solution from the multi-functional catalyst precursor and calcining the multi-functional catalyst precursor to prepare the multi-functional catalyst. The multifunctional catalyst may comprise a first metal catalyst and a second metal catalyst supported on a zeolite support.

Contacting the pyrolysis oil with the multifunctional catalyst at the above reaction conditions may convert at least some of the multi-ring aromatic compounds in the pyrolysis oil to one or more C6 to C8 aromatic compounds. At least some of the multi-ring aromatics converted to one or more C6 to C8 aromatics comprise at least 30%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80% of the multi-ring aromatics in the pyrolysis oil. % may be included. The C6 to C8 aromatic compound may include, but is not limited to, one or more of benzene, toluene, ethylbenzene, xylene, or combinations thereof. In some embodiments, contacting the pyrolysis oil with the multifunctional catalyst at the reaction conditions converts at least some of the multi-ring aromatics in the pyrolysis oil to C6 to C8 aromatics in a single step without performing a subsequent chemical reaction step. can be converted

Contacting the pyrolysis oil with the multifunctional catalyst may be performed at a reaction temperature in a range similar to the reaction temperature for a process for upgrading pyrolysis oil using a commercially available catalyst prepared using conventional metal catalyst precursors. . In some embodiments, the pyrolysis oil may be contacted with the multifunctional catalyst at a reaction temperature of 500° C. or less, 450° C. or less, or even 400° C. or less. The pyrolysis oil may be contacted with the multifunctional catalyst at a reaction temperature of at least 350°C, at least 380°C or even at least 400°C. In some embodiments, the pyrolysis oil is 350 °C to 500 °C, 350 °C to 450 °C, 350 °C to 400 °C, 380 °C to 500 °C, 380 °C to 450 °C, 380 °C to 400 °C,

It may be contacted with the multifunctional catalyst at a reaction temperature of 400°C to 500°C or 400°C to 425°C.

Contacting the pyrolysis oil with the multifunctional catalyst may be performed at a reaction pressure lower than the reaction pressure required to upgrade the pyrolysis oil using commercially available catalysts prepared using conventional metal catalyst precursors. In some embodiments, the pyrolysis oil can be contacted with the multifunctional catalyst at a reaction pressure of less than 6 MPa, less than or equal to 5 MPa, or even less than or equal to 4 MPa. In some embodiments, the pyrolysis oil may be contacted with the multifunctional catalyst at a reaction pressure of at least 0.1 MPa, at least 1 MPa, or even at least 2 MPa. In some embodiments, the pyrolysis oil is multifunctional at a reaction pressure of 0.1 MPa to 5 MPa, 0.1 MPa to 4 MPa, 1 MPa to 5 MPa, 1 MPa to 4 MPa, 2 MPa to 5 MPa, or even 2 MPa to 4 MPa. may be contacted with the catalyst.

In some embodiments, the method of upgrading the pyrolysis oil can further include separating the upgraded pyrolysis oil from the multifunctional catalyst. Separating the upgraded pyrolysis oil from the multifunctional catalyst may be performed using any known method or process for separating fluids from particulate solids.

Upgrading the pyrolysis oil by contacting the multifunctional catalyst of the present disclosure prepared using a heteropolyacid is upgrading the pyrolysis oil by contacting it with a commercially available catalyst prepared using a conventional metal catalyst precursor. can produce higher yields of C6 to C8 aromatics, such as one or more of benzene, toluene, ethylbenzene, xylene, or combinations thereof, compared to In some embodiments, upgrading the pyrolysis oil by contacting the pyrolysis oil with the multifunctional catalyst of the present disclosure prepared using a heteropoly acid is 30 based on the total weight of the upgraded pyrolysis oil separated from the multifunctional catalyst. C6 to C8 aromatics can be prepared in a combined yield of at least 32 wt%, or even at least 35 wt%.

Example

The following examples illustrate the methods of the present disclosure for preparing multifunctional catalysts for upgrading pyrolysis oils and methods for upgrading pyrolysis oils using the multifunctional catalysts. The examples relate in any way to a particular mass flow rate, stream composition, temperature, pressure, time on stream, amount of catalytic metal on a zeolite support or other variable fixed for the purpose of conducting the experiment. Nor are they intended to limit the scope of the present disclosure.

Comparative Example 1: Nano-beta zeolite support

For Comparative Example 1, beta zeolite support particles having no metal compound deposited on either the outer surface or the pore surface were provided as a baseline comparison. Note that beta zeolite itself provides at least some activity to promote cracking of hydrocarbons. The beta zeolite support of Comparative Example 1 was CP814E nano-beta zeolite obtained from Zeolyst International. The nano-beta zeolite support particles had a ratio of 25 divided by the molar amount of silica (SiO ₂ ) by the molar amount of alumina (Al ₂ O ₃ ).

Comparative Example 2: Comparative catalyst for upgrading pyrolysis oil

For Comparative Example 2, a comparative catalyst comprising a first catalytic metal and a second catalytic metal deposited on the outer surface and pore surface of a nano-beta zeolite support was prepared using a conventional metal precursor without heteropolyacid. The first metal catalyst precursor was ammonium molybdate tetrahydrate having the formula [(NH ₃ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] obtained from Sigma-Aldrich. The second metal catalyst precursor was cobalt(II) nitrate hexahydrate having the formula [Co(NO ₃ ) ₂ .6H ₂ O] also obtained from Sigma-Aldrich. The nano-beta zeolite catalyst support was the nano-beta zeolite catalyst support of 1 in comparison.

The comparative catalyst of Comparative Example 2 was prepared by putting 10 g of the nano-beta zeolite catalyst support of Comparative Example 1 in a round bottom flask. Solution A was prepared by dissolving 3.08 g of [(NH ₃ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] in 50 milliliters (mL) of distilled water. Then, solution B was prepared by dissolving 2.65 g of a second metal catalyst precursor [Co(NO ₃ ) ₂ .6H ₂ O] in 50 mL of distilled water. The amounts of [(NH ₃ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] and [Co(NO ₃ ) ₂ .6H ₂ O] were respectively 3% by weight of CO and 12% by weight of Mo in the comparative catalyst of Comparative Example 2 It was chosen to provide the final metal loading. Solution A and solution B were then mixed together and added to the nano-beta zeolite catalyst support in a round bottom flask. The combined solution and the nano-beta zeolite catalyst support were mixed for 2 hours. Water was removed from the nano-beta zeolite catalyst support impregnated with the first and second metal catalyst precursors at a temperature of 50° C. under vacuum, and the solid sample was dried at a temperature of 100° C. overnight. Then, the solid sample was calcined at a temperature of 500° C. for 5 hours to obtain a comparative catalyst of Comparative Example 2.

Comparative Example 3: Comparative phosphorus-containing catalyst for upgrading pyrolysis oil

For Comparative Example 3, a comparative phosphorus-containing catalyst comprising a first catalytic metal, a second catalytic metal and phosphorus deposited on the outer surface and pore surface of the nano-beta zeolite support was prepared using a conventional metal precursor without heteropolyacid. prepared. The first metal catalyst precursor was ammonium molybdate tetrahydrate having the formula [(NH ₃ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] obtained from Sigma-Aldrich. The second metal catalyst precursor was cobalt(II) nitrate hexahydrate having the formula [Co(NO ₃ ) ₂ .6H ₂ O] also obtained from Sigma-Aldrich. The nano-beta zeolite catalyst support was the nano-beta zeolite catalyst support of Comparative Example 1. Phosphoric acid (H ₃ PO ₄ ) obtained from Sigma-Aldrich was used to incorporate phosphorus.

The comparative phosphorus-containing catalyst of Comparative Example 3 was prepared by placing 10 g of the nano-beta zeolite catalyst support of Comparative Example 1 in a round bottom flask. Solution A was prepared by dissolving 3.08 g of the first metal catalyst precursor [(NH ₃ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] in 50 milliliters (mL) of distilled water. Then, solution B was prepared by dissolving 2.65 g of a second metal catalyst precursor [Co(NO ₃ ) ₂ .6H ₂ O] in 50 mL of distilled water. The amounts of [(NH ₃ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] and [Co(NO ₃ ) ₂ .6H ₂ O] were respectively 3% by weight of CO and 12% by weight of Mo in the comparative catalyst of Comparative Example 3 It was chosen to provide the final metal loading. Then, solution A and solution B were mixed together, and 0.15 g of phosphoric acid was dissolved in the combined solution to prepare solution C. Solution C was then added to the nano-beta zeolite catalyst support in a round bottom flask and mixed for 2 hours. Water was removed from the nano-beta zeolite catalyst support impregnated with the first and second metal catalyst precursors at a temperature of 50° C. under vacuum, and the solid sample was dried at a temperature of 100° C. overnight. Then, the solid sample was calcined at a temperature of 500° C. for 5 hours to obtain a comparative phosphorus-containing catalyst of Comparative Example 3.

Example 4: Multifunctional Catalyst for Upgrading Pyrolysis Oils Made Using Heteropolyacids.

In Example 4, a multifunctional catalyst comprising a first metal catalyst, a second metal catalyst and phosphorus deposited on the outer surface and the pore surface of a nano-beta zeolite support according to the present disclosure was prepared by preparing a first metal catalyst precursor. It was prepared using a heteropoly acid for The first metal catalyst precursor was a phosphomolybdic heteropolyacid having the formula [H ₃ PMo ₁₂ O ₄₀ ] obtained from Sigma-Aldrich. The second metal catalyst precursor was cobalt(II) nitrate hexahydrate having the formula [Co(NO ₃ ) ₂ .6H ₂ O] also obtained from Sigma-Aldrich. The nano-beta zeolite catalyst support was the nano-beta zeolite catalyst support of Comparative Example 1.

The multifunctional catalyst of Example 4 was prepared by placing 10 g of the nano-beta zeolite catalyst support of Comparative Example 1 in a round bottom flask. Solution A was prepared by dissolving 2.89 g of the heteropolyacid [H ₃ PMo ₁₂ O ₄₀ ] of the first metal catalyst precursor in 50 milliliters (mL) of distilled water. Then, solution B was prepared by dissolving 2.24 g of a second metal catalyst precursor [Co(NO ₃ ) ₂ .6H ₂ O] in 50 mL of distilled water. The amounts of the first metal catalyst precursor and the second metal catalyst precursor were calculated to give the same metal loading (3 wt % CO and 12 wt % Mo) as the comparative catalysts of Comparative Examples 2 and 3. Then solution A and solution B were mixed together and added to the nano-beta zeolite catalyst support in a round bottom flask. The combined solution and the nano-beta zeolite support were mixed for 2 hours. Water was removed from the nano-beta zeolite catalyst support impregnated with the first and second metal catalyst precursors at a temperature of 50° C. under vacuum, and the solid sample was dried at a temperature of 100° C. overnight. The solid sample was then calcined at a temperature of 500° C. for 5 hours to obtain the multifunctional catalyst of Example 4.

Example 5: Pyrolysis Oil Upgrade

In Example 5, the model pyrolysis oil composition was upgraded using the comparative catalysts of Comparative Examples 1, 2 and 3, and the multifunctional catalyst of Example 4 to prepare at least benzene, toluene, ethylbenzene and xylene. 1-methylnaphthalene obtained from Sigma-Aldrich was used as a model pyrolysis oil.

Referring to FIG. 3 , an apparatus 100 for performing an upgrade of a model pyrolysis oil is schematically illustrated. Apparatus 100 included a fixed bed reactor 110 with catalyst loaded in zone 111 . The fixed bed reactor 110 was maintained in a hot box 112 to maintain the fixed bed reactor 110 at a constant temperature. A liquid feed 116 comprising model pyrolysis oil (1-methylnaphthalene) was introduced into the fixed bed reactor 110 using a liquid pump 120 . Hydrogen 118 and nitrogen 119 may also be added to the liquid feed 116 upstream of the fixed bed reactor 110 . The temperature of the liquid feed 116 was adjusted prior to passing the liquid feed 116 through the heat exchanger 130 and passing it to the fixed bed reactor 110 . The liquid feed 116 was contacted with the catalyst in the fixed bed reactor 110, which contacted at least the model pyrolysis oil (1-methylnaphthalene) to react to upgrade the model pyrolysis oil to at least benzene, toluene, ethylbenzene. and a liquid product stream 114 comprising xylene. The operating conditions of the fixed bed reactor 110 are described in Table 1.

The liquid product stream 114 was passed from the fixed bed reactor 110 to a liquid gas separator 140 , wherein the liquid product stream 114 was passed to a gas fraction 142 comprising constituents of lower boiling point temperatures, and a higher boiling point temperature. It was separated into a boiling fraction and a liquid fraction 144 containing unreacted model pyrolysis oil (1-methylnaphthalene). The composition of liquid fraction 144 was analyzed. Gas fraction 142 was transferred to on-line gas chromatography for compositional analysis of gas fraction 142 . The compositions of gas fraction 142 and liquid fraction 144 were then used to determine the yield of each constituent of liquid product stream 114 . The yields of each compound prepared in the fixed bed reactor for each catalyst of Comparative Examples 1 to 3 and Example 4 are sequentially provided in Table 1. In Table 1 the yield of each component is given in weight percent based on the total mass flow rate of the liquid product stream 114 .

As shown in Table 1, the multifunctional catalyst of Example 4 provided the best performance for upgrading the model pyrolysis oil (1-methylnaphthalene) to benzene, toluene, ethylbenzene and xylene (BTEX). The total BTEX yield obtained using the multifunctional catalyst of Example 4 was 36.7%, which is an improvement of more than 34% over the comparative catalyst of Comparative Example 2. The multifunctional catalyst of Example 4 also yielded the highest total conversion of 1-methylnaphthalene. Thus, at the same temperature and pressure, the multifunctional catalyst of the present application provides a higher yield of BTEX compound at a lower pressure compared to a conventional catalyst used to upgrade pyrolysis oil. Although Example 4 contained phosphorus, the multifunctional catalyst of Example 4 still exhibited lower catalyst acidity than the comparative catalyst of Comparative Example 2 without phosphorus. Therefore, the reduced acidity provided by the structure of the heteropolyacid used as the first metal catalyst precursor in the multifunctional catalyst of Example 4 can increase the yield of BTEX compared to the comparative catalysts of Comparative Examples 2 and 3.

In a first aspect of the present disclosure, a method of preparing a multifunctional catalyst for upgrading a pyrolysis oil comprises contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor. The first metal catalyst precursor, the second metal catalyst precursor, or both may comprise a heteropolyacid. The contacting step may deposit the first metal catalyst precursor and the second catalyst precursor on the outer surface and the pore surface of the zeolite support to prepare a multifunctional catalyst precursor. The method comprises the steps of removing excess solution from the multifunctional catalyst precursor and calcining the multifunctional catalyst precursor to include at least a first metal catalyst and a second metal catalyst deposited on the outer and pore surfaces of a zeolite support. It may further comprise the step of preparing a catalyst.

In a second aspect of the present disclosure, a multifunctional catalyst for upgrading a pyrolysis oil is prepared by a process comprising contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor. and a multifunctional catalyst, wherein the first metal catalyst precursor, the second metal catalyst precursor, or both comprise a heteropolyacid. The contacting step may deposit the first metal catalyst precursor and the second catalyst precursor on the outer surface and the pore surface of the zeolite support to prepare a multifunctional catalyst precursor. The process may further comprise removing the excess solution from the multifunctional catalyst precursor and calcining the multifunctional catalyst precursor to prepare the multifunctional catalyst. The multifunctional catalyst prepared by the present process may comprise at least a first metal catalyst and a second metal catalyst deposited on the outer surface and the pore surface of the zeolite support.

A third aspect of the present disclosure may include any one of the first aspect or the second aspect, wherein the heteropolyacid is at least one metal selected from cobalt, molybdenum, vanadium or a combination thereof and phosphorus, silicon, arsenic or these at least one heteroatom selected from a combination of

A fourth aspect of the present disclosure may include any one of the first to third aspects, wherein the first metal catalyst precursor comprises a heteropolyacid.

A fifth aspect of the present disclosure may include any one of the first to fourth aspects, wherein the first metal catalyst precursor comprises a first heteropolyacid, and wherein the second metal catalyst precursor comprises a different agent than the first heteropolyacid. 2 heteropolyacids.

A sixth aspect of the present disclosure may include any one of the first to fifth aspects, wherein the heteropolyacid comprises a phosphomolybdic heteropolyacid having the formula H ₃ PMo ₁₂ O ₄₀ .

A seventh aspect of the present disclosure may include any one of the first to fifth aspects, wherein the first metal catalyst precursor and the second metal catalyst precursor are the same heteropolyacid, and wherein the heteropolyacid is a first metal, a first a second metal different from the metal and at least one heteroatom.

An eighth aspect of the present disclosure may include a seventh aspect, wherein the heteropolyacid comprises decamolybdodicobaltate heteropolyacid.

A ninth aspect of the present disclosure may include any one of the first through eighth aspects, further comprising dehydrating the heteropolyacid prior to contacting the zeolite support with the solution.

A tenth aspect of the present disclosure may include any one of the first to ninth aspects, wherein the multifunctional catalyst precursor is calcined at a temperature of 500 to 600° C. for a time of 4 to 6 hours to form the multifunctional catalyst. to manufacture

An eleventh aspect of the present disclosure may include any one of the first to tenth aspects, wherein the zeolite support comprises nano beta zeolite having an average pore size of 2 μm or less.

A twelfth aspect of the present disclosure may include any one of the first through eleventh aspects, wherein the zeolite support comprises a molar ratio of silica to alumina of from 10 to 70.

A thirteenth aspect of the present disclosure may be a multifunctional catalyst prepared according to any one of the first to twelfth aspects.

A fourteenth aspect of the present disclosure may include any one of the first through thirteenth aspects, wherein the first metal catalyst comprises molybdenum and the second metal catalyst comprises cobalt.

A fifteenth aspect of the present disclosure may include any one of the first to fourteenth aspects, further comprising phosphorus deposited on the exterior surface and the pore surface of the zeolite support.

A sixteenth aspect of the present disclosure may include any one of the first through fifteenth aspects, wherein the multifunctional catalyst has an acidity of less than 10,000 micromolar ammonia/gram (μmol(NH ₃ )/g).

A seventeenth aspect of the present disclosure may include any one of the first to sixteenth aspects, wherein the multifunctional catalyst has an acidity of from 1000 μmol(NH ₃ )/g to 5000 μmol(NH ₃ )/g .

An eighteenth aspect of the present disclosure may include any one of the first through seventeenth aspects, wherein the multifunctional catalyst has a BET surface area of 400 square meters/gram (m ² /g) or less.

A nineteenth aspect of the present disclosure may include any one of the first through eighteenth aspects, wherein the multifunctional catalyst has a BET surface area between 200 m ² /g and 400 m ² /g.

In a twentieth aspect of the present disclosure, the multifunctional catalyst for upgrading pyrolysis oil comprises at least one cobalt compound, at least one molybdenum compound and phosphorus supported on a zeolite support, wherein at least one of a molybdenum compound, a cobalt compound, or phosphorus is provided as a heteropolyacid precursor.

A twenty-first aspect of the disclosure may include a twentieth aspect, wherein the multifunctional catalyst has an acidity of less than 10,000 micromolar ammonia/gram (μmol(NH ₃ )/g).

A twenty-second aspect of the present disclosure may include any one of the twentieth or twenty-first aspect, wherein the multifunctional catalyst has an acidity of from 1000 μmol (NH ₃ )/g to 5000 μmol (NH ₃ )/g .

A twenty-third aspect of the present disclosure may include any one of aspects 20 through 22, wherein the multifunctional catalyst has a BET surface area of 400 square meters/gram (m ² /g) or less.

A twenty-fourth aspect of the present disclosure may include any one of the twentieth to twenty-third aspects, wherein the multifunctional catalyst has a BET surface area of from 200 m ² /g to 400 m ² /g.

A twenty-fifth aspect of the present disclosure may include any one of the twentieth to twenty-fourth aspects, wherein the heteropolyacid comprises a phosphomolybdic heteropolyacid having the formula H ₃ PMo ₁₂ O ₄₀ .

A twenty-sixth aspect of the present disclosure may include any one of the twentieth to twenty-fifth aspects, wherein the heteropolyacid comprises decamolybdodicobaltate heteropolyacid.

A twenty-seventh aspect of the present disclosure may include any one of the twenty-sixth aspects, wherein the zeolite support comprises nano beta zeolites having an average pore size of 2 μm or less.

A twenty-eighth aspect of the present disclosure may include any one of the twentieth to twenty-seventh aspects, wherein the zeolite support comprises a molar ratio of silica to alumina of from 10 to 70.

In a twenty-ninth aspect of the present disclosure, a method for upgrading a pyrolysis oil comprises subjecting the pyrolysis oil to a multifunctional catalyst at mild reaction conditions comprising a reaction temperature of less than 50 degrees Celsius (°C) and a pressure of less than 6 megapascals (MPa). and contacting with The pyrolysis oil may include multi-ring aromatics. The multifunctional catalyst may be prepared by a process comprising contacting a zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, the first metal catalyst precursor, the second metal catalyst precursor, or Both include heteropolyacids. The contacting step may deposit the first metal catalyst precursor and the second catalyst precursor on the outer surface and the pore surface of the zeolite support to prepare a multifunctional catalyst precursor. The process for preparing the multi-functional catalyst may further include removing the excess solution from the multi-functional catalyst precursor and calcining the multi-functional catalyst precursor to prepare the multi-functional catalyst. The multifunctional catalyst comprises at least a first metal catalyst and a second metal catalyst supported on a zeolite support. Contacting the pyrolysis oil with the multifunctional catalyst at the above reaction conditions converts at least some of the multi-ring aromatics in the pyrolysis oil to one or more C6 to C8 aromatics.

A thirtieth aspect of the present disclosure may include the twenty-ninth aspect, wherein the C6 to C8 aromatic compound comprises one or more of benzene, toluene, ethylbenzene, xylene, or combinations thereof.

A thirty-first aspect of the present disclosure may include the twenty-ninth or thirtieth aspect, wherein the step of contacting the pyrolysis oil with the multifunctional catalyst at the reaction conditions comprises multi- in the pyrolysis oil in a single step without a subsequent chemical reaction step. Some of the ring aromatics are converted to C6 to C8 aromatics.

A thirty-third aspect of the present disclosure may include any one of aspects 29 through 31, wherein contacting the pyrolysis oil with the multifunctional catalyst yields a yield of C6 to C8 aromatics of at least 30%. .

A thirty-fourth aspect of the present disclosure may include any one of the twenty-ninth to thirty-third aspects, further comprising separating the upgraded pyrolysis oil from the multifunctional catalyst.

A thirty-fifth aspect of the present disclosure may include any one of the twenty-ninth to thirty-fourth aspects, wherein the pyrolysis oil is contacted with the multifunctional catalyst at a temperature of 300°C to 450°C.

A thirty-sixth aspect of the present disclosure may include any one of the twenty-ninth to thirty-fifth aspects, wherein the pyrolysis oil is contacted with the multifunctional catalyst at a pressure of 0.1 MPa to 5 MPa.

A thirty-seventh aspect of the present disclosure may include any one of the twenty-ninth to thirty-sixth aspects, wherein the heteropolyacid is at least one metal selected from cobalt, molybdenum, vanadium, or combinations thereof and phosphorus, silicon, arsenic or these at least one heteroatom selected from a combination of

A thirty-eighth aspect of the present disclosure may include any one of the twenty-ninth to thirty-seventh aspects, wherein the first metal catalyst precursor comprises a heteropolyacid.

A thirty-ninth aspect of the present disclosure may include any one of the twenty-ninth to thirty-eighth aspects, wherein the first metal catalyst precursor comprises a first heteropolyacid, and wherein the second metal catalyst precursor comprises a different agent than the first heteropolyacid. 2 heteropolyacids.

A fortieth aspect of the present disclosure may include any one of the twenty-ninth to thirty-ninth aspects, wherein the heteropolyacid comprises a phosphomolybdic heteropolyacid having the formula H ₃ PMo ₁₂ O ₄₀ .

A forty-first aspect of the present disclosure may include any one of the twenty-ninth to thirty-ninth aspects, wherein the first metal catalyst precursor and the second metal catalyst precursor are the same heteropolyacid, and wherein the heteropolyacid is a first metal, a first a second metal different from the metal and at least one heteroatom.

A forty-two aspect of the present disclosure may include a forty-first aspect, wherein the heteropolyacid comprises decamolybdodicobaltate heteropolyacid.

A forty-third aspect of the present disclosure may include any one of aspects 29 through 42, further comprising dehydrating the heteropoly acid prior to contacting the zeolite support with the solution.

A forty-fourth aspect of the present disclosure may include any one of aspects 1 to 43, wherein the multifunctional catalyst precursor is calcined at a temperature of 500 to 600° C. for a time of 4 to 6 hours to obtain the multifunctional catalyst. manufacture

A forty-fifth aspect of the present disclosure may include any one of aspects 29 through 44, wherein the zeolite support comprises a nano beta zeolite having an average pore size of 2 um or less.

A forty-six aspect of the present disclosure may include any one of aspects 29 through 45, wherein the zeolite support comprises a molar ratio of silica to alumina of from 10 to 70.

A forty-seven aspect of the present disclosure may include any one of aspects 29 through 46, wherein the first metal catalyst comprises molybdenum and the second metal catalyst comprises cobalt.

A forty-eighth aspect of the present disclosure may include any one of aspects 29 through 47, further comprising phosphorus deposited on the exterior surface and the pore surface of the zeolite support.

A forty-ninth aspect of the present disclosure may include any one of aspects 21-48, wherein the multifunctional catalyst has an acidity of less than 10,000 micromolar ammonia/gram (μmol(NH ₃ )/g).

A fiftieth aspect of the present disclosure may include any one of aspects 29 to 49, wherein the multifunctional catalyst has an acidity of from 1000 μmol(NH ₃ )/g to 5000 μmol(NH ₃ )/g .

A fiftieth aspect of the present disclosure may include any one of the twenty-ninth to fifty aspects, wherein the multifunctional catalyst has a BET surface area of 400 square meters/gram (m ² /g) or less.

A fifty-two aspect of the present disclosure may include any one of aspects 29 to 51, wherein the multifunctional catalyst has a BET surface area from 200 m ² /g to 400 m ² /g.

A multifunctional catalyst for upgrading pyrolysis oil, a method for preparing a multifunctional catalyst for upgrading a pyrolysis oil using a heteropolyacid as a metal catalyst precursor, and a method for upgrading a pyrolysis oil using the method are described, It should now be understood that this aspect may be used in conjunction with various other aspects.

Throughout this disclosure, various properties and characteristics of the multifunctional catalyst and ranges for various processing parameters and operating conditions for methods for preparing the multifunctional catalyst and upgrading the pyrolysis oil are provided. Where more than one explicit range is provided, it will be understood that subranges and individual values formed within the range are also intended to be provided, preventing provision of all possible combinations of the explicit item. For example, a given range of 1 to 10 can also be formed within the given limits such as 1 to 8, 2 to 4, 6 to 9, and 1.3 to 5.6, as well as individual values such as 1, 2, 3, 4.2 and 6.8. inclusive of all ranges.

It should be apparent to those skilled in the art that various changes and modifications may be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Accordingly, this specification is intended to cover the modifications and variations of the various embodiments described, provided they come within the scope of the appended claims and their equivalents.

Claims (15)

A method for preparing a multifunctional catalyst for upgrading pyrolysis oil, the method comprising:
contacting the zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, wherein the first metal catalyst precursor, the second metal catalyst precursor or both comprise a heteropolyacid, the contacting The step comprises depositing a first metal catalyst precursor and a second catalyst precursor on the outer surface and the pore surface of the zeolite support to prepare a multifunctional catalyst precursor;
removing excess solution from the multifunctional catalyst precursor; and
calcining the multifunctional catalyst precursor to produce a multifunctional catalyst comprising at least a first metal catalyst and a second metal catalyst deposited on the outer surface and the pore surface of the zeolite support. The method of claim 1, wherein the heteropoly acid is
at least one metal selected from cobalt, molybdenum, vanadium, or a combination thereof; and
at least one heteroatom selected from phosphorus, silicon, arsenic, or combinations thereof. The method of claim 1 , wherein the first metal catalyst precursor comprises a first heteropolyacid and the second metal catalyst precursor comprises a second heteropolyacid that is different from the first heteropolyacid. The method of claim 1 , wherein the heteropolyacid comprises a phosphormolybdic heteropolyacid having the formula H ₃ PMo ₁₂ O ₄₀ . 3. The method of claim 1 or 2, wherein the first metal catalyst precursor and the second metal catalyst precursor are the same heteropolyacid, the heteropolyacid comprising a first metal, a second metal different from the first metal, and at least one heteroatom , method. 6. The method of claim 5, wherein the heteropolyacid comprises decamolybdodicobaltate heteropolyacid. 7. The method according to any one of claims 1 to 6, wherein the zeolite support comprises nano beta zeolite having an average pore size of 2 μm or less and a molar ratio of silica to alumina of 10 to 70. A multifunctional catalyst prepared by the method of any one of claims 1 to 7. The multifunctional catalyst of claim 8 , wherein the first metal catalyst comprises molybdenum and the second metal catalyst comprises cobalt. 10. The multifunctional catalyst according to claim 8 or 9, further comprising phosphorus deposited on the outer surface and the pore surface of the zeolite support. 11. The multifunctional catalyst according to any one of claims 8 to 10, wherein the multifunctional catalyst has an acidity of less than 10,000 micromolar ammonia/gram (μmol(NH ₃ )/g). 12. The multifunctional catalyst according to any one of claims 8 to 11, wherein the multifunctional catalyst has a BET surface area of 400 square meters/gram (m ² /g) or less. A method for upgrading pyrolysis oil, said method comprising:
contacting the pyrolysis oil with the multifunctional catalyst at mild reaction conditions comprising a reaction temperature of less than 500 degrees Celsius (°C) and a pressure of less than 6 megapascals (MPa);
The pyrolysis oil comprises a multi-ring aromatic compound, the multifunctional catalyst comprising:
contacting the zeolite support with a solution comprising at least a first metal catalyst precursor and a second metal catalyst precursor, wherein the first metal catalyst precursor, the second metal catalyst precursor, or both comprise a heteropolyacid, wherein the contacting comprises: depositing a first metal catalyst precursor and a second catalyst precursor on an outer surface and a pore surface of a zeolite support to prepare a multifunctional catalyst precursor;
removing excess solution from the multifunctional catalyst precursor; and
prepared by a process comprising calcining a multifunctional catalyst precursor to produce a multifunctional catalyst;
The multifunctional catalyst comprises at least a first metal catalyst and a second metal catalyst supported on a zeolite support,
and contacting the pyrolysis oil with the multifunctional catalyst at the reaction conditions converts at least a portion of the multi-ring aromatics in the pyrolysis oil to one or more C6 to C8 aromatics. 14. The method of claim 13, wherein the contacting of the pyrolysis oil with the multifunctional catalyst under the reaction conditions converts some of the multi-ring aromatics in the pyrolysis oil to C6 to C8 aromatics in a single step without performing a subsequent chemical reaction step. How to convert. 15. The process according to claim 13 or 14, wherein the pyrolysis oil is contacted with the multifunctional catalyst at a temperature of 300°C to 450°C.

Images